Bis(2-carb­oxy-N-{[1-(2-hy­droxy­eth­yl)-3,3-dimethyl­indolin-2-yl­idene]methyl­imino}­anilinium) sulfate monohydrate

Gainsford, G.J.; Ashraf, M.; Kay, A.J.

doi:10.1107/S1600536813003188

Volume 69
Part 3
Pages o343-o344
March 2013

Received 14 January 2013
Accepted 30 January 2013
Online 6 February 2013

Key indicators
Single-crystal X-ray study
T = 153 K
Mean (C-C) = 0.007 Å
H completeness 96%
Disorder in main residue
R = 0.053
wR = 0.152
Data-to-parameter ratio = 9.9
Details

Bis(2-carboxy-N-{[1-(2-hydroxyethyl)-3,3-dimethylindolin-2-ylidene]methylimino}anilinium) sulfate monohydrate

Graeme J. Gainsford,^a ^* Mohamed Ashraf ^b and Andrew J. Kay ^b

^aCarbohydrate Chemistry Group, Industrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand, and ^bPhotonics Group, Industrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
Correspondence e-mail: g.gainsford@irl.cri.nz

The asymmetric unit of the title compound, 2C₂₀H₂₂N₃O₃⁺·SO₄^2-·H₂O, contains four cations, two sulfate anions and two lattice water molecules. One of the four cations shows a different conformation of the hydroxyethyl group; the remaining three are all essentially superimposable. Two cations exhibit two-site orientational disorder [ratios = 0.524 (5):0.476 (5) and 0.616 (6):0.384 (6)] of the last two atoms of their hydroxyethyl groups, and one water molecule is disordered over two positions in a 0.634 (13):0.366 (13) ratio. Each imine H atom is intramolecularly in contact with the adjacent carboxyl O atom, forming an S(6) motif, while all the carboxylic acid H atoms are hydrogen bonded to O atoms of the sulfate anions. Other notable hydrogen-bond interactions involve (methylene, phenyl and imine chain) C-HO (sulfate and carboxyl) and O-HO(water) contacts, making up a comprehensive three-dimensional network involving D₂²(n), with n = 4-6 and 15-16, and C₂²(17) classical hydrogen-bond motifs. The crystal investigated was twinned by pseudomerohedry with a twin component ratio of 0.4745 (12):0.5255 (12).

Related literature

For details of a related synthesis, see: Bhuiyan et al. (2011). For a closely related structure, see: Gainsford et al. (2013). For hydrogen-bonding motifs, see: Bernstein et al. (1995).

Experimental

Crystal data

2C₂₀H₂₂N₃O₃⁺·SO₄^2-·H₂O
M_r = 816.88
Triclinic, $[P \overline 1]$
a = 12.2530 (9) Å
b = 14.6114 (3) Å
c = 23.2442 (4) Å
= 71.681 (1)°
= 87.688 (2)°
= 82.627 (7)°
V = 3917.9 (3) Å³
Z = 4
Cu K radiation
= 1.33 mm^-1
T = 153 K
0.68 × 0.40 × 0.24 mm

Data collection

Rigaku Spider diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.66, T_max = 1.0
24005 measured reflections
10558 independent reflections
9283 reflections with I > 2(I)
R_int = 0.044
_max = 58.9°

Refinement

R[F² > 2(F²)] = 0.053
wR(F²) = 0.152
S = 1.10
10558 reflections
1069 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.52 e Å^-3
_min = -0.53 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O32A-H3A0O101	0.84	1.94	2.644 (8)	140
O2-H2OO14	0.84	1.66	2.457 (5)	158
N1-H1NO1	0.70 (5)	2.08 (5)	2.652 (5)	139 (6)
O3-H3OO13ⁱ	0.84	1.97	2.792 (5)	165
N101-H11NO101	0.97 (5)	1.90 (5)	2.642 (6)	132 (4)
N201-H21NO201	0.90 (5)	1.89 (6)	2.626 (6)	138 (5)
O203-H23OO701ⁱⁱ	0.84	1.95	2.741 (6)	157
N301-H31NO301	0.96 (5)	1.95 (5)	2.654 (5)	129 (4)
O102-H102O21ⁱⁱⁱ	0.84	1.68	2.509 (5)	169
O202-H202O13^iv	0.84	1.81	2.565 (5)	149
O302-H302O22^v	0.84	1.77	2.562 (6)	157
C8-H8O11^vi	0.95	2.55	3.402 (6)	150
C12B-H12CO301	0.99	2.41	3.37 (2)	164
C15-H15O12ⁱ	0.95	2.29	3.143 (6)	149
C19-H19BO11^vi	0.99	2.39	3.357 (7)	166
C20-H20BO201^vi	0.99	2.41	3.343 (6)	157
C220-H22BO1^vi	0.99	2.48	3.456 (6)	168
C39-H39BO23	0.99	2.53	3.514 (7)	175
C108-H108O24	0.95	2.26	3.073 (6)	143
C114-H114O102^vii	0.95	2.54	3.323 (7)	139
C115-H115O23^v	0.95	2.39	3.202 (7)	143
C205-H205O21^v	0.95	2.57	3.359 (7)	141
C208-H208O12	0.95	2.26	3.119 (5)	150
C212-H212O80A	0.95	2.60	3.486 (10)	156
C215-H215O11^vi	0.95	2.27	3.137 (7)	152
C306-H306O203^viii	0.95	2.36	3.154 (7)	140
C308-H308O23	0.95	2.39	3.278 (6)	155
C315-H315O24ⁱⁱⁱ	0.95	2.26	3.150 (6)	156
Symmetry codes: (i) x, y+1, z; (ii) x-1, y, z; (iii) -x+1, -y+1, -z+1; (iv) -x, -y, -z; (v) -x+1, -y, -z+1; (vi) -x, -y+1, -z; (vii) x, y-1, z; (viii) x+1, y, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: FSProcess in PROCESS-AUTO (Rigaku, 1998); data reduction: FSProcess in PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2718 ).

Acknowledgements

We thank the MacDiarmid Institute for Advanced Materials and Nanotechnology for funding of the diffractometer equipment and the NZ Foundation for Research, Science & Technology for funding.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.
Bhuiyan, M., Delower, H., Ashraf, M., Teshome, A., Gainsford, G. J., Kay, A. J., Asselberghs, I. & Clays, K. (2011). Dyes Pigm. 89, 177-187.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.
Gainsford, G. J., Ashraf, M. & Kay, A. J. (2013). Unpublished work.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku (2005). CrystalClear. Rigaku Americas Corporation, The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.

organic compounds